Lubricating compositions



Unite States Patent Patented July 2, 1957 LUBRICATING coMPosrrIoNs Frank A. M. Buck, Martinez, and George T. Coker, 512,

Concord, Calif., assignors to Shell Development Company, New York, N. Y., a corporation of Delaware No Drawing. Application September 27, 1954, Serial No. 458,666

3 Claims. (Cl. 25232.7)

This invention relates to new and improved liquid and sohd hydrocarbon compositions such as fuels, lubricating oils and greases. More particularly, the invention relates limited due to the fact that they tend to deplete rapidly,

so that their effectiveness is of short duration.

It has now been discovered that the depletion rate of these organic phosphorus-containing additives can be reduced by addition, to compositions containing them, a minor amount of an oil-soluble N-hydrocarbyl-substituted polyamine salt of an acidic compound such as an organic or an inorganic acid, the hydrocarbyl radical of which is preferably a long alkyl group of at least and preferably containing about between 12 and 18 carbon atoms. The combination of such amine salts with oilsoluble phosphorus-containing compounds not only prolongs the life of a lubricating composition containing such additives under various conditions of use such as under high temperature and load conditions in various types of engines, including diesel engines, internal combustion engines and the like, but the additive combination exhibits a synergistic effect resulting in lubricating compositions having enhanced anti-corrosion, anti-sludge, and anti-wear properties.

The phosphorus-containing compounds include salts of 4 products is also contemplated and they are obtained by neutralizing the indicated reaction products with oxides, hydroxides, carbonates, or halides of monovalent or polyvalent metals such as the alkali, alkaline earth or heavy metals exemplified by Na, K, Ca, Ba, Sr, Mg, Al, Zn, Pb, Ni, as well as of organic nitrogen bases, to form the corresponding salts and mixtures thereof. Compounds of this type include salts such as Na Ca, Ba, Zn and Al or amine (di-Z-ethylhexylamine, octadecylamine) salts of alkyl, cycloalkyl, alkaryl, aralkyl, and aryl phosphates and thiophosphates. Specific illustrative substances are Na, K, Ca, Ba, Zn and Al, di-Z-ethylhexylamine or cyclohexylamine salts of methylcyclohexyl acid phosphate, dimethylcyclohexyl dithiophosphatc, dihexyl acid thiophosphate, lauryl benzyl acid thiophosphate, butyl trichloro methane phosphonic acid; Pass-olefin reaction product,

2 2,486,188; 2,261,047; 2,540,084; 2,358,305; 2,466,408; 2,344,393; 2,493,217; and 2,662,856 as Well as the nonsalt or non-neutralized products, such as PzSs-terpene reaction products and mixtures thereof. Compounds of this type are available commercially under the trade names of Lubri-Zol 304 (Lubri-Zol Corp); Aerolube (American Cyanamid Co.); Stan-Add 48 (Standard Oil Co. of Indiana); Santolube 394-0 (Monsanto Chemical Co.). Other phosphorus compounds which can be used are of the type described by Smalheer et al. in Petroleum Processing, December 1952, as well as mixtures thereof.

The phosphorus-containing compounds should be used in amounts based on the total composition not in excess of about 5% by weight and preferably from about 1% to about 2% by Weight.

The N-hydrocarbylor N,N'-dihydrocarbyl-substituted polyamine salt which activates, improves and in general exhibits a synergistic effect in combination with phosphorus compounds of the above type can be more specifically defined as being an N- or N,N'-hydrocarbyl-substituted polyamine salt of an organic or inorganic acid, the hydrocarbyl radical in the cationic portion of said salt being a straight or branched, saturated or unsaturated radical containing at least 10 and preferably from about 12 to 18 carbon atoms. The polyamines which can be used to form the salts include N-C12-18 alkylpropylenediamine, N-ClZ-IS alkyl ethylenediamine, N-n-dodecylpropylenediamine, N-n-tetradecylpropylenediamine, N-noctadecylpropylenediamine, N- 2-ethylhexyl -propylenediamine, N-cyclohexylpropylenediamine, N,Ndidodecylpropylenediamine, N-tetradecyltripropylenetetramine; N- octylethylenediamine, N n dodecyldiethylenetriamine, N-n-tetradecyldiethylenetriamine, N-n-hexadecyltriethylenetetramine, N-phenylpropylenediamine, N-oleylpropylenediamine, etc.

Some of the amines of this type are available commercially under the trade name Duomeens (Armour Chemical) and include Duomeen 12, Duomeen C, Duomeen S and Duomeen T.

Acids used to combine with the above-mentioned polyamines to form the salts include aliphatic acids, aromatic acids, alicyclic acids, organic compounds containing inorganic acid radicals such as organic sulfonic acids and organic compounds containing inorganic phosphorus acid radicals. The aliphatic acids can be saturated or un saturated, monoor polycarboxylic acids, saturated aliphatic monocarboxylic acids being exemplified by capiic, lauric, myristic, palmitic, stearic acids; unsaturated aliphatic monocarboxylic acids exemplified by oleic, ricinoleic, linoleic, linolenic acids; aliphatic polycarboxylic acids such as alkylsuccinic, alkylmaleic, alkylsebasic, alkyladipic, alkyltartaric, and alkylcitric acids; miscellaneous acids derived from oxidation of hydrocarbons such as paraflin Waxes; or fatty oils containing substantial amounts of free fatty acids such as soya bean oil, peanut oil, rape seed oil, tallow, horse fat, etc. Aromatic acids include benzoic, salicyclic, cinnamic, phthalic acids and derivatives thereof such as diisopropyl salicyclic acid, C14-18-21lkY1S31lCYCllO acids, diwaxbenzoic acid. Illustrative examples of cyclic acids are naphthenic acids, abietic acid, cyclohexylacetic acid, cyclohexylbutyric acid and the like. The organic compounds containing inorganic acids include: (a) organic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, triisopropyl-naphthalenesulfonic acid, diphenylsulfonic acid, polyamylnaphthalenesulfonic acid, diwaxbenzenesulfonic acid, xylenesulfonic acid, benzenedisulfonic acid, waxsulfosuccinic acid, diwaxnaphthalenesulfonic acid, petroleumsulfonic acids derived from various petroleum fractions such as: gas oil, kerosene, light oil, turbine oil, mineral lubricating oil, petroleum waxes, petrolatum, etc.; (b) phosphorus-containing acids, such as obtained by reacting PzSs, P205,

P4S3,'and the like with olefinic hydrocarbons, aromatic hydrocarbons, phenolic compounds, alcohols, and organic acids as listed above and mixtures thereof.

Specific polyamine salts which can be used in compositions of this invention include: N-n-dodecyl propylene diamine mono and dioleate, N-n-octadecylpropylene diamine, mono and dioleate, N-n-octadecylpropylene diamine mono and dioleate, N-n-octadecyl propylene diamine stearate, N-n-octadeeyl propylene diamine petroleum sulfonate, N-cyclohexylpropylene diarnine di octyl dithio phosphate, N-N-octadecyl phenyl propylene diamine adipate, N-n-lauryl ethylene diamine oleate, N- n-octadecyl ethylene diamine diricinoleate, N-n-octyl diethylene triamine oleate, Duorneen-T-rnono and dioleate, Duorneen-T-adipate (Armour Chemical) and mixtures thereof.

The polyamine salt can be used in amounts of from about 0.01% to about 2% and preferably from about 0.1% to about 1% by weight.

The above additive combination, namely, the combina tion of organic phosphorus-containing compound and the polyamine salt is particularly effective in lubricating compositions containing detergent sulfonates and/ or phenates. The additive combination of the invention functions as an activator for the sulfonates and phenates.

The sulfonates can be neutral and/or basic oil-soluble sulfonates derived from any suitable material and prepared by any of the wellknown suitable methods. Preferred materials for making oil-soluble sulfonates include mineral lubricating oil fractions, alkyl-substituted aromatic compounds and alkyl-substituted polar containing aromatic compounds. Petroleum sulfonates suitable for use in compositions of this invention are described in United States Patents 2,280,419, 2,344,988, 2,361,804, 2,375,222, 2,480,638, 2,485,861, 2,509,863, 2,501,731, 2,523,582 and 2,585,520. The sulfonates can be purified by the methods described in United States Patents 2,441,258 and 2,488,721. Suitable aromatic sulfonates include those described in United States Patents 2,411,583, 2,418,894, 2,442,915, 2,483,501, 2,531,324, 2,556,108 and 2,556,848. Although various metal sulfonates are contemplated in the practice of the invention, including alkali metal sulfonates, alkaline earth metal sulfonates (including magnesium) and other polyvalent metal sulfonates, particularly other divalent metal sulfonates and trivalent metal sulfonates, the sulfonates of the metals of group II of the periodic table and having an atomic number from 12 to 56, inclusive, the preferred, and especially of the alkaline earth metals within that group of metals. Specific sulfonates which are particularly suitable for use in compositions of this invention include oil-soluble metal sulfonates such as Na, K, Li, Ca, Ba, Mg, Zn, Al, In, Sn, Cr and Co petroleum sulfonate, tetratertiarybutylnaphthalene sulfonate, diwaxbenzenesulfonate, stearylbenzenesulfonate, diwaxnaphthalenesulfonate, diisobutylenephenolsulfonate, tertiary-octylphenol sulfonate, ditertiary-amylphenol sulfonate, alkylateddibenzothiophene sulfonate and mixtures thereof.

The phenates suitable for use in compositions of this invention include those described in United States Patents 2,197,833, 2,228,654, 2,280,419, 2,344,988, 2,361,804, 2,410,652, 2,501,991, 2,501,992 and 2,610,982. Specifically, they can be either simple phenates such as metal alkylphenates (Ca-cetylphenate), polar substituted simple phenates (Ca or Zn alkylsalicylates) or polyphenates such as where a plurality of the simple phenates are condensed at positions ortho and/ or para to the phenolic hydroxy group through alkylidene (methylene) radicals or other suitable divalent non-metallic radicals, such as sulfur or selenium. Although various metal phenates are contemplated in the practice of the invention including mono and polyvalent metal phenates, such as the alkali, alkaline earth and heavy metal phenates of which preferred are the polyvalent metal phenates of the metals of group H 4 of the periodic table and having an atomic number from 12 to 56, especially the alkaline earth metals within that group of metals. Illustrative compounds are: Na, K, Li, Ca, Ba, Sr, Mg, Zn, Al, Cd, Ni, Fe, Co cetyl phenate, dibutyl phenate, C14-18-Sa1iCYlat, octyl thiophenate, cyclohexyl phenate, cetyl phenol sulfide, waxyl phenate, as well as the above metal salts of the condensation product of alkyl phenol with formaldehyde, acetaldehyde or ben- Zaldehyde, e. g., Ca, Ba or Mg salts of octyl phenolforrnaldehyde condensation product ranging in molecular Weight of from 500 to 1,100.

When the detergent sulfonates and/or phenates are used in lubricating compositions of this invention they are generally present in amounts of from 0.01% to 15% by weight.

Lubricating bases for additives of this invention can be any natural or synthetic hydrocarbonaceous material having lubricating properties. Thus, the base may be a hydrocarbon oil of wide viscosity range, e. g., .100 SUS at F. to SUS at 210 F. The hydrocarbon oils may be blended with fixed oils such as castor oil, lard oil and the like, and/or with synthetic lubricants such as polymerized olefins, copolymers of alkylene glycols and oxides; organic esters of polybasic organic and inorganic acids, e. g., di-2-ethylhexyl sebacate, dioctyl phthalate, trioctyl phosphate; polymeric tetrahydrofuran; polyalkyl silicone polymer, e. g., dimethyl silicone polymer and the like.

Representative mineral lubricating oils utilized in evaluating the utility of the present additives had the following specifications:

Gravity, API Pour Point, "F

Fuel oils which are greatly improved with respect to color, anti-clogging tendencies and the like by the addition thereto of a minor amount of additives of this invention are of the type described in U. S. Patents 2,639,227 and 2,672,408.

Various types of natural and synthetic thickened greases such as soap silica gel or clay thickened greases can be greatly improved with respect to stability and corrosion inhibition by addition to such greases of a minor amount of a polyamine salt of this invention. Wax and wax compositions also can be improved in the same manner by means of these amines.

Compositions of this invention are illustrated by the following formulations:

Composition A Percent weight Basic Ca-petroleum sulfonate (oil-soluble) 2.07 Mixture of Zn-dimethylcyclohexyl dithiophosphate and Pzss-terpene reaction product in the ratio of 5:1, respectively 1.4 N-Ci2 ia-alkylpropylenediamine dioleate 0.5 Mineral lubricating oil Balance Composition B Basic Ca-petroleum sulfonate (oil-soluble) 2.07 Mixture of Zn-dimethylcyclohexyl dithiophosphate and PzSs-terpene reaction product in the ratio of 5 :1, respectively 1.4 N-C12-1a-alkylpropylenediamine monooleate 0.5

Mineral lubricating oil Balance Other examples of compositions of this invention are tabulated therein below:

An efiective way of shipping, handling and utilizing the additive combination of this invention is to form a Components 1 Primary Additives:

(1) 0a dimethylcyclohexyl thlophosphate Ba dicresyl dithiophosphate Zn dimethylcyclohexyl thiophosphate Zn dioetyl phosphate K salt of PQSBOIBfl-H polymer P s terpene reaction prod- I10 Trieresyl phosphate. N-Cna alkylpropylenediamine dioleate N-laurylpropylene-diamine dioleate..-. N-octadecylpropylene d1- amine dipetroleum sultonate N-oleylethylene-diamine adipate N,N-cyclohexyl ethylenediamine stearate Optional Additives:

Ga petroleum sult'onate Ba petroleum su].tonate.. Ba diwax benzene sulionat Zn petroleum sulionate Ca salt of oetyl phenol-formaldehyde condensation pr Ca cetyl phenete. Ba diamyl phenol sulfide. Octadecylamine Phenyl-a-naphthylamm Oil-1B alkyl succinic acid 2,6-ditertbutyl-4-rnethyl phenoL Base Lubricant: Mineral lubricating oil 1 Each of the additives can be added to the base lubricant in amounts of from 0.1% to 5% by weight.

The outstanding properties of lubricating compositions of this invention are demonstrated from the results obtained when tested in (I) a Cadillac engine under conditions described in the Havely et a1. SAE Preprint of March 24, 1954, entitled Influence of Lubricant and Material Variables on Cam and Tappet Surface Distress; (II) Timken extreme pressure lubricant tester [(Timken index mixture of the organic-phosphorus compound and polyamine salt in the ratio of 5:1 to 1:5 and preferably 3:1 respectively and which mixture can be dispersed in amounts of from 20 to 4% in a suitable base carrier such as a light hydrocarbon oil. The mixture or concentrate can be added when necessary and in proper proportions to the base which is to be improved such as fuel oils, lubricating oils, greases, waxes and the like.

Compositions of this invention can be modified by addition thereto of minor amounts (0.015%) of pour point depressants, viscosity index improver, blooming agents, corrosion inhibitors, oiliness agents, solubilizers, and the like. Among such materials can be included high molecular weight polymers, e. g., Acryloide, which are polymeric esters of methacrylic acid and coconut fatty acids, wax naphthalene condensation products, isobutylene polyconstant temperature for 24 hours after which the iron mers, alkyl styrene polymers; inorganic and organic specimen is examined for rust. nitrites, such as NaNOz or LiNOz and di-isopropylam TEST RESULTS Tests I II 111 IV Oil sample New Oil from Lauson A pearance of Bulk Oil engine, En- Composition liter Face Temp. 25 gine Bulk Relative in Cadillac F., Cup Oil tern Corrosion Engine Rotated at 125 F., up Rate 800 R. P. M. rotated at 800 R. P. M.

(1) Mineral oil Very poor-- 5 (2) Mineral 011 +24% Basic Ca Petroleum sulionate do 5 14 d6 (3) Mineral oil +1.9% of a Zn dirnethyl cyclohexyl Borderline 24 76 dithiophosphate. (4) Mineral oil +1.4% of 5:1 mixture of Zn dimethyl Satisfactory. 45 17 76 cycliheryl dithiophosphate +P3S5 terpene to no (5 Mineral oil +2% Ca petroleum sulionate +1.8% Very poor. 5

Ca salt of octyl phenol-formaldehyde condensation product. (6) 5+0.4% Zn dibuty1dithiocarbamate.. 5 (7) 5+1.3% PzSi terpene reaction product- 19 (8)di2-1|-O.t5% O a-Ora alkyl propylene diamine Very poor 4 0 ea e. (9) Composition A (present invention) Satisfactory. 38 31 45 (10) Composition B (present invention) do 38 31 45 monium nitrite or dicyclohexylammonium nitrite, organic sulfides, e. g., wax disulfide ethylene bistolyl sulfide, amine, e. g., octadecylamine and the like, Also, phenolic antioxidants such as 2,6-ditertiary-4-methyl phenol and 2,2- methylene bis(4-metl1yl-6-tertiarybutylphenol) can be used in conjunction with the additive combination of this invention.

We claim as our invention:

l. A lubricating composition comprising a major amount of a mineral lubricating oil containing about.

2-5% of an oil-soluble basic calcium petroleum sultonate, about l-2% of a mixture of zinc dirnethylcyclohexyl dithiophosphate and a PzSs-terpene-reaction product in the ratio of 5-1 respectively, and about 0.5-l% of N-C12-1a alkyl propylene diamine oleate.

2. A lubricating oil composition comprising a major amount of a mineral lubricating oil and containing about 2% basic calcium petroleum sulfonate, about 1.4% of a mixture of zinc dimethyl cyclobexyl dithiophosphate and P255 terpene reaction product in the ratio of 5:1 respectively and about 0.5% of N-C121s alkyl propylene diamine dioleate.

P285 terpene reaction product in the ratio of 5:1 respectively and about .5 of N-C121a alkyl propylene diamine oleate.

References Cited in the file of this patent UNITED STATES PATENTS 2,261,047 Asseff Oct. 28, 1941 2,382,699 Duncan Aug. 14, 1945 2,417,876 Lewis Mar. 25, 1947 2,493,216 Berger et al. Jan. 3, 1950 2,493,483 Francis et a1. Jan. 3, 1950 2,662,856 Bishop Dec. 15, 1953 2,689,846 Beegle Sept. 21, 1954 2,723,235 Asseif Nov. 8, 1955 20 2,736,658 Pfohl Feb. 28, 1956 

1. A LUBRICATING COMPOSITION COMPRISING A MAJORR AMOUNT OF A MINERAL LUBRICATING OIL CONTAINING ABOUT 2-5% OF AN OIL-SOLUBLE BASIC CALCIUM PETROLEUM SULFONATE, ABOUT 1-2% OF A MIXTURE OF ZINC DIMETHYLCYCLOHEXYL DITHIOPHOSPHATE AND A P2S5-TERPENE-REACTION PRODUCT IN THE RATIO OF 5-1 RESPECTIVELY, AND ABOUT 0.5-1% OF N-C12-18 ALKYL PROPYLENE DIAMINE OLEATE. 